Conversion of dicarboxylic acids to monomers and plasticizers

ABSTRACT

The present disclosure relates to a composition that includes a first repeat unit defined by 
                         
where R includes a first hydrocarbon chain that includes at least one olefinic bond, R 5  includes a second hydrocarbon chain, the second hydrocarbon chain may be saturated, and n may be between 2 and 1,000.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional PatentApplication No. 62/805,042 filed Feb. 13, 2019, the disclosure of whichis incorporated herein by reference in its entirety.

CONTRACTUAL ORIGIN

This invention was made with government support under Contract No.DE-AC36-08GO28308 awarded by the Department of Energy. The governmenthas certain rights in the invention.

SUMMARY

An aspect of the present disclosure is a composition that includes afirst repeat unit defined by

where R includes a first hydrocarbon chain that includes at least oneolefinic bond, R₅ includes a second hydrocarbon chain, the secondhydrocarbon chain may be saturated, and n may be between 2 and 1,000. Insome embodiments of the present disclosure, the first hydrocarbon chainmay be between 3 and 10 carbon atoms. In some embodiments of the presentdisclosure, the first hydrocarbon chain may further include at least onealkyl group. In some embodiments of the present disclosure, the alkylgroup may include at least one of a methyl group, an ethyl group, apropyl group, and/or a butyl group.

In some embodiments of the present disclosure, the composition mayfurther include a second repeat unit defined by,

where R* includes a third hydrocarbon chain that may be saturated orunsaturated, R₅* includes a fourth hydrocarbon chain, the fourthhydrocarbon chain may be saturated, and m may be between 2 and 1,000.

In some embodiments of the present disclosure, the composition mayfurther include a third repeat unit defined by,

where R** includes a fifth hydrocarbon chain that may be saturated orunsaturated, R₅** includes a sixth hydrocarbon chain, the sixthhydrocarbon chain may be saturated, and o may be between 2 and 1,000.

In some embodiments of the present disclosure, the composition may be

An aspect of the present disclosure is a composition that includes afirst repeat unit defined by

where R₃ includes a first hydrocarbon chain comprising at least onesulfur containing functional group, R₅ includes a second hydrocarbonchain, the second hydrocarbon chain may be saturated, and n may bebetween 2 and 1,000. In some embodiments of the present disclosure, thefirst hydrocarbon chain may include between 3 and 10 carbon atoms. Insome embodiments of the present disclosure, the first hydrocarbon chainmay further include at least one alkyl group. In some embodiments of thepresent disclosure, the alkyl group may include at least one of a methylgroup, an ethyl group, a propyl group, and/or a butyl group.

In some embodiments of the present disclosure, the composition mayinclude

In some embodiments of the present disclosure, the composition mayfurther include a second repeat unit defined by

where R₃* includes a third hydrocarbon chain that may or may not includeat least one sulfur containing functional group, R₅* includes a fourthhydrocarbon chain, the fourth hydrocarbon chain may be saturated, and mmay be between 2 and 1,000.

In some embodiments of the present disclosure, the composition mayfurther include a third repeat unit defined by

where R₃** includes a fifth hydrocarbon chain that may or may notinclude at least one sulfur containing functional group, R₅** includes asixth hydrocarbon chain, the sixth hydrocarbon chain may be saturated,and o may be between 2 and 1,000.

An aspect of the present disclosure is a composition that includes

where R includes a first hydrocarbon chain, R includes a secondhydrocarbon chain, and R² includes a third hydrocarbon chain. In someembodiments of the present disclosure, at least one of R, R¹, and/or R²may be saturated. In some embodiments of the present disclosure, atleast one of R, R¹, and/or R² may be unsaturated. In some embodiments ofthe present disclosure, at least one of R, R¹, and/or R² may be astraight chain having between 3 and 10 carbon atoms.

In some embodiments of the present disclosure, the composition may havethe structure

In some embodiments of the present disclosure, the composition may havethe structure

BRIEF DESCRIPTION OF THE DRAWINGS

Some embodiments are illustrated in referenced figures of the drawings.It is intended that the embodiments and figures disclosed herein are tobe considered illustrative rather than limiting.

FIG. 1 illustrates the temperature dependent degradation of homopolymersand/or copolymers containing modified bioderived dicarboxylic acidrepeat units, according to some embodiments of the present disclosure.

FIG. 2 illustrates the physical properties of polymers made frombioderived dicarboxylic acids, according to some embodiments of thepresent disclosure.

FIGS. 3 and 4 illustrate reaction routes to bioderived,dicarboxylic-based materials that may be used as plasticizers, accordingto some embodiments of the present disclosure.

FIG. 5 illustrates a comparison of the plasticizing potential of variousmaterials, including plasticizers derived from bioderived dicarboxylicacids, according to some embodiments of the present disclosure.

DETAILED DESCRIPTION

The embodiments described herein should not necessarily be construed aslimited to addressing any of the particular problems or deficienciesdiscussed herein. References in the specification to “one embodiment”,“an embodiment”, “an example embodiment”, “some embodiments”, etc.,indicate that the embodiment described may include a particular feature,structure, or characteristic, but every embodiment may not necessarilyinclude the particular feature, structure, or characteristic. Moreover,such phrases are not necessarily referring to the same embodiment.Further, when a particular feature, structure, or characteristic isdescribed in connection with an embodiment, it is submitted that it iswithin the knowledge of one skilled in the art to affect such feature,structure, or characteristic in connection with other embodimentswhether or not explicitly described.

As used herein the term “substantially” is used to indicate that exactvalues are not necessarily attainable. By way of example, one ofordinary skill in the art will understand that in some chemicalreactions 100% conversion of a reactant is possible, yet unlikely. Mostof a reactant may be converted to a product and conversion of thereactant may asymptotically approach 100% conversion. So, although froma practical perspective 100% of the reactant is converted, from atechnical perspective, a small and sometimes difficult to define amountremains. For this example of a chemical reactant, that amount may berelatively easily defined by the detection limits of the instrument usedto test for it. However, in many cases, this amount may not be easilydefined, hence the use of the term “substantially”. In some embodimentsof the present invention, the term “substantially” is defined asapproaching a specific numeric value or target to within 20%, 15%, 10%,5%, or within 1% of the value or target. In further embodiments of thepresent invention, the term “substantially” is defined as approaching aspecific numeric value or target to within 1%, 0.9%, 0.8%, 0.7%, 0.6%,0.5%, 0.4%, 0.3%, 0.2%, or 0.1% of the value or target.

As used herein, the term “about” is used to indicate that exact valuesare not necessarily attainable. Therefore, the term “about” is used toindicate this uncertainty limit. In some embodiments of the presentinvention, the term “about” is used to indicate an uncertainty limit ofless than or equal to ±20%, ±15%, ±10%, ±5%, or ±1% of a specificnumeric value or target. In some embodiments of the present invention,the term “about” is used to indicate an uncertainty limit of less thanor equal to ±1%, ±0.9%, ±0.8%, ±0.7%, ±0.6%, ±0.5%, ±0.4%, ±0.3%, ±0.2%,or ±0.1% of a specific numeric value or target.

The present disclosure relates to unsaturated dicarboxylic acids, forexample muconic acid and/or a alkylated muconic acid, produced from theconversion of aromatic compounds such as phenols and/or cresols, and theconversion of these unsaturated dicarboxylic acids to useful polymersand/or polymer additives. As shown herein, alkylated unsaturateddicarboxylic acids, e.g. methylated muconic acid, can act as a moreefficient plasticizer than adipic acid and the extra methyl group canresult in higher hydrophobicity in the target polymer utilizing theplasticizer. Furthermore, the olefinic bonds (carbon-carbon doublebonds) in unsaturated dicarboxylic acids, e.g. muconic acid, can bemodified to introduce other advantages in the final targeted polymer(e.g. further permeability reduction, flame resistance groups, etc.).Note that as used herein, the term “muconate” can be used to refer tothe esters or salts of the muconic acids (in which muconic acid is thefree-acid/protonated molecule 2,4-hexadienedioic acid (2,4-HAD)).Another aspect of the present disclosure is the synthesis of saturatedand unsaturated DCAs from alkylated phenol compounds, which may then beused to produce the novel monomers and polymers described herein.

In general, the present disclosure relates to reacting the double bondspresent in unsaturated dicarboxylic acids (DCAs), e.g. withthiol-containing molecules, to functionalize the DCAs, before the DCAsare reacted with other molecules (e.g. a diamine) to make largermolecular weight products (e.g. polymers). Or, in some embodiments ofthe present disclosure, the DCA may be first reacted with othermolecules (e.g. a diamine) to make larger molecular weight products(e.g. polymers) such that the DCA double bonds are present in the largermolecule, so that they may be subsequently reacted with other molecules(e.g. thiol-containing molecules) to further modify the larger molecularweight products.

Structure 1 and Structure 2 illustrate exemplary structures of DCAs,muconic acid (i.e. 2,4-HAD) and a methylated muconic acid,2-methyl-2,4-hexadienedioic acid, respectively, which may be used toproduce novel polymers and/or plasticizers as described below.

Structures 1 and 2 can be represented by the generalized structure below(Structure 3):

For the case of a simple straight chain positioned between twocarboxylic acid groups, e.g. muconic acid (Structure 1), R includes atleast one carbon-carbon double bond. The straight-chained (unbranched)muconic acid is an example of a C6 dicarboxylic acid for which R isequal to four carbon atoms, including two carbon-carbon double bonds inthe chain. Other examples (other than muconic acid) of unbranched,straight-chained, bioderived dicarboxylic acids, containing at least oneolefinic bond, are shown below in Scheme 1. This list is provided forillustrative purposes and is not limiting. For example, longer chainedDCAs containing one or more olefinic bonds are considered within thescope of the present disclosure.

Thus, referring again to Structure 3, in some embodiments of the presentdisclosure, R may be an unbranched carbon chain having between 2 and 5carbon atoms inclusively, containing one or two carbon-carbon doublebonds.

For the case of a branched straight chain positioned between twocarboxylic acid groups e.g. 2-methyl-2,4-hexadienedioic acid (Structure2), in addition to the at least one carbon-carbon double bond, R mayalso include at least one alkyl group; e.g. a methyl group, an ethylgroup, a propyl group, a butyl group, etc. The methylated muconic acidof Structure 2 is an example, now referring to Structure 3, of a C6dicarboxylic acid for which R is equal to four carbon atoms, includingtwo carbon-carbon double bonds and a methyl group. Thus, in someembodiments of the present disclosure, R may be between 2 and 5 carbonatoms, inclusively, and may contain one or two carbon-carbon doublebonds, where R₁ (see below) is an alkyl group, either straight-chainedor branched, with between 1 and 10 carbon atoms. Examples of branched,olefinic DCAs, within the scope of the present disclosure, include thoseshown in Scheme 2 below. This list is provided for illustrative purposesand is not limiting. For example, longer chained DCAs containingbranched hydrocarbon chains having one or more olefinic bonds areconsidered within the scope of the present disclosure. Also, althoughnot shown in Scheme 2, in some embodiments of the present disclosure, abranched, olefinic DCA may contain more than when alkyl group.

Thus, from Schemes 1 and 2, and referring to generalized Structure 3, Rmay include between 2 and 5 carbon atoms, positioned between the twocarboxyl end groups, and R may or may not have a functional groupattached to it, as represented by R₁ in Scheme 2. In some embodiments ofthe present disclosure, R₁ may be an aromatic and/or a simplehydrocarbon and/or it may contain other elements including for example,oxygen, nitrogen, phosphorous, and/or sulfur. So, R₁ may be constructedof elements other than carbon and hydrogen. Referring to the list ofexamples above, specific examples of R₁ according to some embodiments ofthe present disclosure include a methyl group, but may also include aheteroatom-containing groups such as chlorine or fluorine, and/or acarboxylic acid.

As stated above, the double bonds of an unsaturated DCA provide usefulreaction sites that may be utilized to make unique intermediates and/orproducts. For example, unsaturated 2,4-HDA (Structure 1) may be reactedwith a sulfur-containing reactant such as butanethiol or thiophenol toproduce compounds like that shown in Structure 4 and Structure 5:

Thus, R₂ may include an aromatic and/or an alkyl group, a simplehydrocarbon, and/or R₂ may contain other elements including for example,oxygen, nitrogen, phosphorous, and/or sulfur. Referring to Structure 4,specific examples of R₂, according to some embodiments of the presentdisclosure, include at least one of a methyl group, an ethyl group, anaromatic group, a phosphate group and/or a butyl group. Thus, ingeneral, the carbon-carbon double bonds contained in R of generalizedStructure 3 may be reacted with a thiol group to produce generalizedStructure 6,

where R₃ may be a straight or branched, unsaturated or partiallyunsaturated, chain having at least one sulfur-containing functionalgroup. According to some embodiments of the present disclosure, specificexamples where R₃ is a sulfur-functionalized straight chain positionedbetween the two carboxylic acid groups are summarized in Scheme 3 below,where R₄ may be, for example, an aromatic functional group, for examplea benzene ring, an alkyl side chain, a dithiol (to cross link multiplechains), a carboxylic acid, a hydroxyl, an alkyl side chain containinghalogens (e.g. chlorine, fluorine, etc.) and/or other heteroatoms andtheir respective oxides (e.g. phosphorous or phosphorus oxides). Themolecules shown in Scheme 3 are shown for illustrative purposes and arenot limiting.

According to some embodiments of the present disclosure, referring againto Structure 6, examples where R₃ is a sulfur-functionalized branchedchain positioned between two carboxylic acid groups are summarized inScheme 4 below. For example, R₄ may be an aromatic functional group, forexample a benzene ring an alkyl side chain, a dithiol (to cross linkmultiple chains), a carboxylic acid, a hydroxyl, an alkyl side chaincontaining halogens (e.g. chlorine, fluorine, etc.) or other heteroatomsand their respective oxides (e.g. phosphorous or phosphorus oxides). Themolecules shown in Scheme 4 are shown for illustrative purposes and arenot limiting.

In some embodiments of the present disclosure, an unsaturated DCA, e.g.2,4-HDA, may be reacted by Diels-Alder Reactions to produce a moleculelike that shown for Structure 7:

where Structure 7 may be reacted as described below, like the other DCAsdescribed herein, to produce novel polymers and or plasticizers.

In addition, in some embodiments of the present disclosure, thecarbon-carbon double bonds (as shown in Schemes 1 and 2) may beconverted to saturated bonds by hydrogenation. For the example of2,4-HDA, the 2,4-HDA may be hydrogenated to produce hexanedioic acid.Thus, in some embodiments of the present disclosure, any of thestructures represented by Structure 3 and illustrated in Schemes 1 and 2may be saturated (i.e. any carbon-carbon double bonds have beenhydrogenated) or partially saturated/unsaturated (e.g. functionalizedwith a sulfur-containing groups, while still containing at least onecarbon-carbon double bond).

Structures 4-6 and Schemes 3 and 4 provide examples of products made byreacting the carbon-carbon double bonds of saturated DCAs (e.g. 2,4-HDA)before the DCA framework is incorporated into larger molecular weightmolecules (e.g. polymers). However, in some embodiments of the presentdisclosure, a saturated DCA may first be reacted with another moleculeto produce a larger molecule (e.g. dimer, oligomer, and/or polymer) suchthat the carbon-carbon double bond(s) are maintained in the largermolecule to be reacted in a subsequent reaction or reactions. Reaction 1shows the reaction of 2,4-HDA with a diamine to form a homopolymer,where the carbon-carbon double bonds of the 2,4-HDA repeat unit issubsequently reacted as shown in Reaction 2 with a sulfur-functionalizedbenzene ring to produce a benzene-functionalized homopolymer and/orcopolymer. As defined herein, the product of Reaction 2 is referred toherein as a “homopolymer” when all of the olefinic bonds react to formbenzene functional groups, whereas a polymer containing both unreactedolefinic bonds and some benzene functional groups, in different monomersubunits, is referred to herein as a “copolymer”. Referring to thesereactions, n may be between 2 and 1000, inclusively.

Although Reactions 1 and 2 show the specific reactions of muconic acidwith 1,6-hexanediamine, any of the olefinic DCAs described by Structure3 and illustrated in Schemes 1 and 2 may be reacted with a diamine toproduce a product similar in structure and functionality to that shownin Reaction 1. The general reaction for reacting an olefinic DCA with adiamine is represented by Reaction 3,

where the DCA corresponds to the general structure of a DCA (Structure3) and the diamine may be any diamine where R₅ is a hydrocarbon chain.In some embodiments of the present disclosure, R₅ may be a saturatedhydrocarbon chain having between 1 and 10 carbon atoms. In someembodiments of the present disclosure, R₅ may be a branched hydrocarbonchain having one or more of an alkyl group and/or a functional groupthat include one or more elements other than, or in addition to, carbonand hydrogen. Specific non-limiting examples of diamines suitable forReaction 3 include straight-chained hydrocarbons end-capped with twoamine groups where the chain is a saturated hydrocarbon chain havingbetween 1 and 10 carbon atoms. The generalized product of Reaction 3,the olefinic bonds in particular, may then be reacted with a reactanthaving a thiol group as shown below in generalized Reaction 4,

where R₃ is as defined above for Structure 6 and x corresponds to thenumber of olefinic bonds contained in R.

The product of Reaction 2, as shown herein, has improved temperatureresistance and/or flame resistance. In some embodiments of the presentdisclosure, Reaction 2 was completed by dissolving the olefinic polymerresulting from Reaction 1 in N-methyl-2-pyrrolidone (NMP) and stirringovernight with thiobenzene. FIG. 1 illustrates the thermal gravimetricanalysis of nylon-6,6 compared to a modified nylon having the structureof the product shown in Reaction 2 above. The modified nylon based on2,4-HDA exhibits improved temperature stability over the nylon-6,6.

FIG. 2 compares the glass transition temperatures (T_(g)), meltingpoints (T_(m)), and decomposition temperatures (T_(D,50)) for nylonssynthesized from the equimolar reaction of hexamethyl diamine (HMDA)with carboxylic acids (columns 1-4) to form nylons and two respectivenylons modified post polymerization. Specifically, data is provided forthe nylons in which the carboxylic acids are: 2-methyl muconate(2-methyl-2,4-hexadienedioic acid), 3-methyl muconate(3-methyl-2,4-hexadienedioic acid), a blend 50-50 of 2-methyl muconateand 3-methyl muconate [2-methyl-2,4-hexadienedioic acid and3-methyl-2,4-hexadienedioic acid], and a 25%, 25%, 50% blend of 2-methylmuconate, 3-methyl muconate [2-methyl-2,4-hexadienedioic acid and3-methyl-2,4-hexadienedioic acid], and adipic acid. The left two columnsrefer to a trans-trans muconate control modified with benzenethiol(Reaction 2) and a 25-25-50 blend. FIG. 2 illustrates that the modifiedmethyl muconates possess nylon properties when copolymerized with adipicacid and can be modified to outperform the other nylons with respect tothermal decomposition temperatures, while maintaining the otherrequisite thermal properties. Further thermal properties of selectnylons are reported in Table 2.

TABLE 2 Performance Advantages of Nylons made using Alkylated DCAs2-methyl 3-methyl Adipic muconate muconate T_(g) T_(m) 100 — — 60 260 —100 — −40 140 — — 100 −40 140 —  50  50 −40 140  50  25  25 40 230

Structure 8 illustrates an exemplary structure for anadipate-co-2-methyl muconate-co-2-methyl muconate copolymer made usingthe ratios shown in Table 2. The sum of m, n, and o can range from 2 to1,000 and in the last line of Table 2 m=2n=2o. The homopolymers of themethyl muconates with hexamethyldiamine resulted in a polymer that haslower thermal properties when compared to nylon-6,6. Additionally,copolymers of the 2-methyl and 3-methyl muconates do not exhibit anydifferent performance, enabling the use of mixed 2-methyl muconate and3-methyl muconate streams to produce unique copolymers. When copolymersof methyl muconates and adipic acid were made, an ideal nylon wassynthesized with methyl groups added to enable other performanceenhancements (e.g. lower water permeabilities).

Although Reaction 1-4 illustrate condensation reactions between aminegroups and carboxylic acids to make intermediate polymers containingolefinic groups (Reactions 1 and 3), followed by reacting the olefinicgroups with a thiol-functionalized reactant to make the final products(Reactions 2 and 4), in some embodiments, the order may be reversed. Forexample, in a first reaction, the olefinic groups of muconic acid mayfirst be reacted with a thiol-functionalized reactant. This may then befollowed by a second reaction between the carboxylic acid groups of thenow functionalized molecule with a diamine to produce the homopolymerand/or copolymer products shown in Reactions 2 and 4.

Further, according to some embodiments of the present disclosure, thecarboxyl groups of unsaturated DCAs and/or saturated DCAs may becondensed with alcohols to produce unique compounds, diesters, suitablefor use as plasticizers in plastic compositions/blends. Examples ofboth, unsaturated and saturated diesters are shown below in Structure 8and Structure 9.

R¹ and R² may be the same or different. Thus, R¹ and/or R² may includean aromatic and/or an alkyl group, a simple hydrocarbon, and/or R maycontain other elements including for example, oxygen, nitrogen,phosphorous, and/or sulfur. Therefore, any of the dicarboxylic acidsrepresented by Structure 3 and illustrated in Schemes 1 and 2, and theirsaturated equivalents, may be reacted with an alcohol (esterification)to form a diester, which as shown below, may have properties very wellsuited as plasticizers. A generalized reaction for reacting a DCA withan alcohol to produce a diester is shown below in Reaction 5. Again, R₁and R₂ in Reaction 5 may be derived from the same alcohol or a differentalcohol.

Structure 10 and Structure 11 illustrate specific examples of suchdiester plasticizers, such as di(2-ethylhexyl phthalate) (DEHP) anddi(2-ethyl-hexyl) adipate according to some embodiments of the presentdisclosure, where saturated muconic acid and 2-methyl-2,4-hexadienedioicacid were esterified with 2-ethyl hexanol.

FIG. 3 illustrates one embodiment of a reaction route to productplasticizers based on 3-methyl-2,4-hexadienedioic acid Initially, thedicarboxylic acid is converted to an acyl chloride for facile reactivityand subsequently reacted with 2-ethyl hexanol to produce themethyl-muconate plasticizers. Subsequently, the methyl muconateplasticizer can be hydrogenated to make methyl adipate plasticizers.

FIG. 4 illustrates one embodiment of a reaction route to productplasticizers based on 2-methyl-2,4-hexadienedioic acid. Initially, thedicarboxylic acid is converted to an acyl chloride for facile reactivityand subsequently reacted with 2-ethyl hexanol to produce themethyl-muconate plasticizers. Subsequently, the methyl muconateplasticizer can be hydrogenated to make methyl adipate plasticizers.

Table 1 illustrates a comparison of a polyvinyl chloride (PVC) plasticusing either adipic acid as a plasticizer or a methylated DCA as aplasticizer, where each plasticizer was blended with the PVC. Table 1illustrates that reductions in the glass transition temperature (T_(g))may be obtained using alkyl-functionalized DHAs and/or theirhydrogenated, saturated forms.

TABLE 1 T_(g) of PVC as a function of plasticizer loading Diacid Loading(wt. %) T_(g) Adipic 1 90 5 74 Methyl-Muconate 1 89 5 67

FIG. 5 illustrates the glass transition temperature for PVC (virgin PVCin the far left column) and PVC plasticized with 10 wt. % adipic acid,methyl muconic acid, and the 2-ethylhexyl diesters of adipic acid,2-methyl muconic acid, 3-methyl muconic acid, and a 50-50% blend of themethyl muconic esters. The blend of 2 and 3 methyl muconic behaves thesame as the pure methyl-muconate compounds, and the methyl-muconates aretwice as effective at plasticization as the adipic analogue.

An aspect of the present disclosure is the synthesis of saturated andunsaturated DCAs from alkylated phenol compounds. For example,3-methyl-phenol may be converted to 3-methyl-1,2-benzenediol, which maythen be converted to 2-methyl-2-4-hexadienedioic acid (see Structure 2above). Another example is the conversion of 4-methyl-phenol to4-methyl-1,2-benzenediol, which may be subsequently converted to3-methyl-2,4-hexadienedioic acid, Structure 11.

Once made, and as described above, the saturated and/or unsaturated DCAsmay be utilized to produce an array of various molecules, includingfunctionalized monomers, plasticizers, and/or polymers, with examples ofpossible polymers including nylons, and/or polyesters (saturated andunsaturated).

Whether or not a reactant or product described herein is “bioderived”may be determined by analytical methods. Using radiocarbon and isotoperatio mass spectrometry analysis, the bio-based content of materials canbe determined. ASTM International, formally known as the AmericanSociety for Testing and Materials, has established a standard method forassessing the biobased content of carbon-containing materials. The ASTMmethod is designated ASTM-D6866. The application of ASTM-D6866 to derivea “biobased content” is built on the same concepts as radiocarbondating, but without use of the age equations. The analysis is performedby deriving a ratio of the amount of radiocarbon (14C) in an unknownsample to that of a modern reference standard. The ratio is reported asa percentage with the units “pMC” (percent modern carbon). If thematerial being analyzed is a mixture of present-day radiocarbon andfossil carbon (containing no radiocarbon), then the pNMC value obtainedcorrelates directly to the amount of biomass material present in thesample. Thus, ASTM-D866 may be used to validate that the compositionsdescribed herein are and/or are not derived from renewable sources.

EXAMPLES Example 1

A composition comprising: a first repeat unit defined by

wherein: R comprises a first hydrocarbon chain comprising at least oneolefinic bond, R₅ comprises a second hydrocarbon chain, the secondhydrocarbon chain is saturated, and n is between 2 and 1,000.

Example 2

The composition of Example 1, wherein the first hydrocarbon chaincomprises between 3 and 10 carbon atoms.

Example 3

The composition of Example 2, wherein the first hydrocarbon chainfurther comprises at least one alkyl group.

Example 4

The composition of Example 3, wherein the alkyl group comprises at leastone of a methyl group, an ethyl group, a propyl group, or a butyl group.

Example 5

The composition of Example 1, wherein the second hydrocarbon chaincomprises between 3 and 10 carbon atoms.

Example 6

The composition of Example 1, wherein R comprises at least one of

and R₁ comprises an alkyl group.

Example 7

The composition of Example 6, wherein the alkyl group comprises at leastone of a methyl group, an ethyl group, a propyl group, or a butyl group.

Example 8

The composition of Example 1, further comprising: a second repeat unitdefined by,

wherein: R* comprises a third hydrocarbon chain that may be saturated orunsaturated, R₅* comprises a fourth hydrocarbon chain, the fourthhydrocarbon chain is saturated, and m is between 2 and 1,000.

Example 9

The composition of Example 8, further comprising: a third repeat unitdefined by,

wherein: R** comprises a fifth hydrocarbon chain that may be saturatedor unsaturated, R₅** comprises a sixth hydrocarbon chain, the sixthhydrocarbon chain is saturated, and o is between 2 and 1,000.

Example 10

The composition of Example 9, comprising:

Example 11

A composition comprising: a first repeat unit defined by

wherein: R₃ comprises a first hydrocarbon chain comprising at least onesulfur containing functional group, R₅ comprises a second hydrocarbonchain, the second hydrocarbon chain is saturated, and n is between 2 and1,000.

Example 12

The composition of Example 11, wherein the first hydrocarbon chaincomprises between 3 and 10 carbon atoms.

Example 13

The composition of Example 12, wherein the first hydrocarbon chainfurther comprises at least one alkyl group.

Example 14

The composition of Example 13, wherein the alkyl group comprises atleast one of a methyl group, an ethyl group, a propyl group, or a butylgroup.

Example 15

The composition of Example 12, wherein the second hydrocarbon chaincomprises between 3 and 10 carbon atoms.

Example 16

The composition of Example 12, wherein R₃ comprises at least one of

R₁ comprises an alkyl group, and R₄ comprises at least one of anaromatic group, an alkyl group, a dithiol group, a carboxylic acid, ahydroxyl group, or a halogen.

Example 17

The composition of Example 11 comprising:

Example 18

The composition of Example 11, further comprising: a second repeat unitdefined by

wherein: R₃* comprises a third hydrocarbon chain may or may not compriseat least one sulfur containing functional group, R₅* comprises a fourthhydrocarbon chain, the fourth hydrocarbon chain is saturated, and m isbetween 2 and 1,000.

Example 19

The composition of Example 18, further comprising: a third repeat unitdefined by

wherein: R₃** comprises a fifth hydrocarbon chain may or may notcomprise at least one sulfur containing functional group, R₅** comprisesa sixth hydrocarbon chain, the sixth hydrocarbon chain is saturated, ando is between 2 and 1,000.

Example 20

A composition comprising

wherein: R comprises a first hydrocarbon chain, R¹ comprises a secondhydrocarbon chain, and R² comprises a third hydrocarbon chain.

Example 21

The composition of Example 20, wherein at least one of R, R¹, or R² issaturated.

Example 22

The composition of Example 20, wherein at least one of R, R¹, or R² isunsaturated.

Example 23

The composition of Example 20, wherein at least one of R, R¹, or R² is astraight chain having between 3 and 10 carbon atoms.

Example 24

The composition of Example 23, wherein the straight chain furthercomprises at least one alkyl group.

Example 25

The composition of Example 24, wherein the alkyl group comprises atleast one of a methyl group, an ethyl group, a propyl group, or a butylgroup.

Example 26

The composition of Example 20 having the structure

Example 27

The composition of Example 20 having the structure

The foregoing discussion and examples have been presented for purposesof illustration and description. The foregoing is not intended to limitthe aspects, embodiments, or configurations to the form or formsdisclosed herein. In the foregoing Detailed Description for example,various features of the aspects, embodiments, or configurations aregrouped together in one or more embodiments, configurations, or aspectsfor the purpose of streamlining the disclosure. The features of theaspects, embodiments, or configurations, may be combined in alternateaspects, embodiments, or configurations other than those discussedabove. This method of disclosure is not to be interpreted as reflectingan intention that the aspects, embodiments, or configurations requiremore features than are expressly recited in each claim. Rather, as thefollowing claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment, configuration, oraspect. While certain aspects of conventional technology have beendiscussed to facilitate disclosure of some embodiments of the presentinvention, the Applicants in no way disclaim these technical aspects,and it is contemplated that the claimed invention may encompass one ormore of the conventional technical aspects discussed herein. Thus, thefollowing claims are hereby incorporated into this Detailed Description,with each claim standing on its own as a separate aspect, embodiment, orconfiguration.

What is claimed is:
 1. A composition comprising:

wherein: R comprises a hydrocarbon chain having four carbon atoms and anethyl group.
 2. The composition of claim 1, comprising:


3. The composition of claim 1, comprising:


4. The composition of claim 1, wherein R further comprises twocarbon-carbon double bonds.
 5. The composition of claim 4, comprising:


6. A composition comprising: a first repeat unit comprising:

wherein: R comprises a hydrocarbon chain having four carbon atoms, amethyl group, and two carbon-carbon double bonds, and n is between 2 and2,000, inclusively.
 7. The composition of claim 6, wherein the firstrepeat unit comprises


8. The composition of claim 6, wherein the first repeat unit comprises


9. The composition of claim 8, further comprising:

wherein: m is between 2 and 2,000, inclusively.
 10. The composition ofclaim 9, comprising:

wherein: n is between 2 and 2,000, exclusively, and m is between 2 and2,000, exclusively.
 11. A composition comprising: a first repeat unitcomprising:

wherein: n is between 2 and 2,000, inclusively.
 12. The composition ofclaim 11, further comprising: a second repeat unit comprising:

wherein: m is between 2 and 2,000, inclusively.
 13. The composition ofclaim 12, further comprising: a third repeat unit comprising:

wherein: z is between 2 and 2,000, inclusively.
 14. The composition ofclaim 13, comprising:

wherein: n is between 2 and 2,000, exclusively, m is between 2 and2,000, exclusively, and z is between 2 and 2,000, exclusively.